Azodyestuffs insoluble in water and process of making same



Patented Dec. 29, 1931 PATENT OFFICE LEOIPOLD LASKA AND ARTHUR ZITSCHER ASSIGNORS T GENERAL ANILINE W TION OF DELAWARE RKS, ING, OF NEW YORK, N. Y., A CORPORA- OF OFFENBAGH-ON-THE-MAIN, GERMANY,

AZODYESTU'FFS INSOLUBLE IN WATER AND PROCESS OF MAKING SAME No Drawing. Application filed March 1 1929, Serial No. 343,841, and in Germany May 7, 1928.

Our present invention relates to new azodyestuffs which are insoluble in water and yield valuable pigment dyes or fast dyeings and printings, when prepared on the vegetable fiber.

They'are obtained by combining any diazo, tetra-Z0 or diazoazo compound not containing sulfonic 0r carboxylic groups with a 2.(2- hydroxy-3naphthoyl-amino) -5-halogen-1.4ldimethoxy-benzene of the general formula OCH;

on -o O-NHQ Hal The new dyestuffs show better properties of fastness than those prepared from 2-hydroXy 3 naphthoylaminohydroquinonedi methylether described in U. S. Patent No. 1357414. Theentrance of a halogen atom into the para position relative to the arylamino group increases the fastness to light of these new dyestuffs in such a degree that the series of these combinations represents a specific group of dyestuffs particularly fast to light among the remarkably fast dyestuflis prepared from the Q-hydroxy-3-naphthoylarylides. Some of the new dyestufifs produced by our present invention are also distinguished by a considerable fastness to bucking.

In order to further illustrate our invention the -following examples are given, but we wish it to be understood that we are not limited to the particular. products nor reaction conditions mentioned therein:

E$LWZZJZ6 J.14:-2 parts of l-chloro-Q-toluidine are diazotized in the usual manner and the diazo solution is combined with a solution of 37 .6 parts of 2-(2-hydroXy-3-naphthoylamino) -5-chloro-1.t-dimethoxy benzene in a dilute caustic soda solution rinsed with Turkey red oil andan amount of sodium acetate suflicient for binding the excess of the mineral acid. The precipitated dyestuff is filtered off and well washed. It corresponds to the formula:

CH3 It represents, when dry, a red powder soluble in concentrated sulfuric acid with a wine red,

tint. It yields, when treated with a substratum, in the usual manner, advantageously in the form of a paste, red lakes of a very good fastness to light.

Example 2.\Vell boiled and dried cotton, Lyarn is impregnated with a solution containing per liter l grs. of 2. (2-hydroXy-3-naph thoyl amino) 5 chloro 1.4 dimethoxy benzene, 8 cc. of caustic soda solution of 34 B.

and cc. of Turkey red oil. Theyarn, thus treated, is well wrung out and developed with a diazo solution containing per liter 1.62 grs. of 2.5-diehloro-aniline and being neutralized with sodium acetate. The material is rinsed cold and hot and then soaped boiling hot.

In this manner an orange brown dyeing of an excellent fastness to light is obtained. The dyestuff thus produced on the fiber corresponds to the formula:

O CH:

By developing the goods prepared as described above in a diazo solution, which contains per liter 1.42 grs. of 5-chloro-2-aminotoluene and is neutralized with a bicarbonate, a bluish red dyeing is obtained which shows a very good fastness to light and bucking.

E mample 3.-Cotton yarn previously treated in the appropriate manner is impregnated with a solution containing per liter 3.5 grs. of 2. (2-hydroXy-3-naphthoyl-amino) -5-bromo-lA-dimethoxy benzene, 7 cc. of caustic soda solution of 84 B. and 10 cc. of Turkey red oil. The yarn, thus treated, is well hydroextracted and developed with a diazo solution containing per liter 1.52 grs. of 3-n'itrolamino-1-toluene and being neutralized with sodium acetate. Then it is rinsed and soaped boiling hot. In this manner a yellowish claret red dyeing of a very good fastness is obtained. The dyestutf thus produced on the fiber corresponds to the formula:

No, OH 'ooru OMHQB.

O CH:

Meta-xy1idine Bluish red. 3-chloroani1ine 'Brown orange. 4-ch1oro-2-tolnidine Red. 4.6-dich1oro-1.3-t01uidine Yellowisli red. 2.4.5-trichloroaniline Brownish red.

4-ch1oro-2-aminodipheny1ether 5-chlor0-2-aminodiphenylether 2-nitroani1ine 3-nitroani1ine 4-ch1oro-2-nitroaniline 2-cl11oro-4=-nitroaniline 4-nitro-2-toluidine 5-nitr0-2-t01uidine 3-nitro-4-to1uidine 4-nitro-2-anisidine 5nitro-2-anisidine 3-nitro-1A-ani'sidinen l-aminoanthraquinone o-aminoazotoluene 2-pheneto1e-azo-a-naph 11y mine- Dianisidine Yellowish red. Full red. Brownish red. Reddish orange. Reddisn brown. Reddish brown. Yellowish red. Brownish red. Beddish brown. Yellowish red. Brownish claret red. Bluish garnet. Reddish brown. Bluish garnet. Reddish black. Blackish blue.

means everywhere combining in substance or 'on a substratum, especially on the vegetable We claim: 1. As new compounds the azo dyestuffs of the general formula:

OCH:

C O-NH Hal wherein R means an aromatic residue of the benzene, diphenyl, naphthalene or anthracene series not containing sulfonic nor carboxylic groups, which compounds are, when dry, colored powders, insoluble in water, yielding when mixed with substrata valuable color lakes and when prepared on the fiber dyeings and printings of a 'very good fastness especially to light.

2. As new compounds the azo dyestuffs of the general formula:

BOB:

wherein R means a halogenated residue of the benzene series not containing sulfonic nor carboxylic groups, which compounds are when dry colored powders, insoluble in water, yielding when mixed with substrata valuable color lakes and when prepared on the fiber dyeings and printings of a very good fastness especially to light.

. 3. As new compounds the azo dyestuffs of the general formula:

OCH:

OCHa

wherein R means a halogenated residue of the benzene series not containing sulfonic nor carboxylic groups, which compounds are, when dry, colored powders, insoluble in water, yielding when mixedwith substrata valuable color lakes and when prepared on the fiber dyeings and printings of a very good fastness especially to light.

4. As a new compound the azo dyestufi of the formula:

' 01 OH 0cm GONHQC1 which compound is, when dry, an orange brown powder, insoluble in water, yielding Til when mixed with a substratum an orange brown color lake and when prepared on the fiber orange brown dyeings and printings of an excellent fastness especially to light.

5. Materials dyed with the dyestuffs of the general formula:

OCH:

wherein R- means an aromatic residue of the benzene, diphenyl, naphthalene or anthracene series not containing sulfonic nor carboxylic groups, which dyed materials show a very good fastness especially to light.

6. Materials dyed with the dyestuffs of the general formula:

b CHa wherein R means a halogenated residue of the benzene series not containing sulfonic nor carboxylic groups, which dyed materials show a Very good fastness especially to light.

7. Materials dyed with the dyestuffs of the general formula:

OCH; OH o O-NH-OQI b CH3 wherein R means a halogenated residue of the benzene series not containing sulfonic nor carboxylic groups, which dyed materials show a very good fastness especially to light.

8. Materials dyed with the dyestufi' of the formula OCH3 O CH;

which dyed materials show orange brown lshaides of an excellent fastness especially to lg it.

In testimony whereof, we affix our signatures.

LEOPOLD LASKA. ARTHUR ZITSCHER. 

